于九皋
天然大分子修饰改性和功能化及环境友好材料的制备技术和应用开发研究
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- 姓名:于九皋
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学术头衔:
博士生导师
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学科领域:
有机化学
- 研究兴趣:天然大分子修饰改性和功能化及环境友好材料的制备技术和应用开发研究
于九皋,毕业于河北大学化学系。现为天津大学教授、博士生导师。享受国务院政府特殊津贴,国家教委理科化学课指委、教育部化学化工课指委成员,天津市学位委员会化学学科评议组成员,全国降解塑料研究会副理事长。长期从事教学和科研工作,从事专业为应用化学。研究方向为天然大分子修饰改性和功能化及环境友好材料的制备技术和应用开发研究。主持并完成部、委级科研项目12项,在科技成果转化为生产力方面作了大量的工作,并取得显著成绩。其中如以淀粉为原料经氧化成双醛淀粉再经表面微囊化覆醛和稳定化处理后,使其具有治疗氮质血症和尿毒症的尿素氮吸附药“包醛氧淀粉”获国家颁发的新药证书,被列为国家级新药,并获国家教委科技进步二等奖、国家科技进步三等奖。在此基础上引入固定化酶的技术研究开发的新一代产品“吸附尿素氮的胶囊口服剂”获国家发明专利授权。国家“八五”攻关项目“淀粉型光生物可控降解地膜的研究开发”在完成年产两千吨的规模化生产经天津市经委鉴定验收后,获国家计委批准进行万吨级的产业化实施工程。其核心技术堆肥环境自降解塑料的制备方法获发明专利授权。热塑性淀粉塑料是一类可完全降解的塑性材料。作为一种材料尚有许多基础问题要解决,如材料的机械性能、耐水性、淀粉的回晶等问题。近期在应用基础研究方面进行了探索性的研究,也取得一些初步成果。已公开发表研究论文100余篇,其中有40余篇 被SCI、EI收录。获授权发明专利二项。已培养出博士研究生6名、硕士研究生18名。目前有9名博士生、5名硕士生在学。
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【期刊论文】Formamide as the Plasticizer for Thermoplastic Starch
于九皋, Xiaofei Ma, Jiugao Yu
Journal of Applied Polymer Science, Vol. 93, 1769-1773 (2004),-0001,():
-1年11月30日
As a novel plasticizer, formamide was tested in thermoplastic starch (TPS), in which native cornstarch granules were proved to transfer to a continuous phase by scanning electron microscope (SEM) and the hydrogen bond interaction between plasticizer and starch was proved by Fourier transform infrared (FTIR) spectroscopy. Mechanical tests showed that tensile strength and Young's modulus of formamide-plasticized TPS (FPTPS) were lower than glycerol-plasticized TPS (GPTPS) and elongation at break and energy break were higher. The effect of formamide and glycerol on the retrogradation of TPS was studied using X-ray diffractometry. Formamide could effectively restrain the starch retrogradation at three different relative humidity (RH) environments, because it could form the more stable hydrogen bonds with the starch hydroxy group than glycerol. From these results, we found that the elongation at break, energy break, and the retrogradation of TPS were ameliorated by formamide.
thermoplastic starch, formamide, plasticizer, retrogradation
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于九皋, Shujun Wang, Jiugao Yu, Jinglin Yu
Journal of Applied Polymer Science, Vol. 93, 686-695 (2004),-0001,():
-1年11月30日
In the presence of dicumyl peroxide, the compatibility of thermal plasticized starch/linear low-den-sity polyethylene (TPS/LLDPE) blends using maleic anhydride (MAH) as compatibilizer was investigated. The thermal plasticization of starch and its compatibilizing modifi-cation with LLDPE was accomplished in a single-screw extruder at the same time. We prepared three types of blends containing different percentages of TPS and MAH. The content of MAH based on LLDPE was 0, 1, and 2wt%, respectively. The morphology of the blends was studied by SEM. It was found that, with the addition of MAH, the blends have good interfacial adhesion and finely dispersed TPS and LLDPE phases, which is reflected in the mechanicaland thermal properties of the blends. The blends containing MAH showed higher tensile strength, elongation at break, and thermal stability than those of blends without MAH. The rheologic properties of the blends demonstrated the existence of processing. Finally, the dynamic thermal mechanical analysis results indicated that, with the addition of MAH, the compatibility between TPS and LLDPE in the blends was substantially improved.
starch, polyethylene (, PE), , blends, compatibility, rheology
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【期刊论文】A Mixed Plasticizer for the Preparation of Thermoplastic Starch
于九皋, Xiao Fei MA, Jiu Gao YU*, Jin FENG
Chinese Chemical Letters Vol. 15, No. 6, pp 741-744, 2004,-0001,():
-1年11月30日
In this paper, formamide was firstly used as plasticizer to prepare thermoplastic starch (TPS), which could suppress the retrogradation of TPS by X-ray diffractometry (XRD) and show a good flexibility, but was weaker than conventional glycerol-plasticized TPS (GPTPS). When urea was introduced into plasticizer, both the retrogradation and mechanical properties were ameliorated The tensile stress, strain and energy break of TPS plasticized by urea (wt.20%) and formamide (wt.10%), respectively, reached 4.83MPa, 104.6% and 2.17Nm (Newtonּmeter) after it had been stored at relative humidity (RH) 30% for one week.
Thermoplastic starch,, formamide,, urea,, retrogradation.,
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于九皋, 马骁飞, 于九皋**
高分子学报,2004,(2),240~245,-0001,():
-1年11月30日
用甲酰胺作为塑化剂制备了热塑性淀粉(TPS),扫描电镜显示甲酰胺可以使淀粉塑化,形成均一的连续相;流变性能说明在加工温度范围内,甲酰胺塑化淀粉(FPTPS)的剪切应力对温度变化敏感性要小于甘油塑化淀粉(GPTPS);用热重和DSC研究了热稳定性和玻璃化转变; FPTPS在13%~23%的水含量时有较好的力学性能,水含量为13%时,FPTPS最大的断裂强度3.9MPa;水含量为17%时,FPTPS最大的伸长率为95%;与GPTPS 相比,在RH(Relative humidity)=0.50% and 100%环境下,FPTPS 有良好的耐回生性能,这主要是因为甲酰胺可以和淀粉羟基形成更稳妥定的氢健。
热塑性淀粉,, 甲酰胺,, 塑化剂,, 回生
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于九皋, 于九皋a 王少敏*, b
有机化学,2003,23(9)1033~1035,-0001,():
-1年11月30日
利用IR,13C NMR和XPS等技术研究了硝化纤维素(CN-1.15)对肌酐(Cr)的吸附行为,并提出了可能的吸附路线。 光谱分析的结果充分表明,碱性条件下,CN-1.15对Cr的吸附是通过碱化的硝酸酯基与Cr的胍基碳生成离子复合物而达到的。
IR,, 13C NMR,, XPS,, 肌酐,, 吸附机理
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于九皋, 杨冬芝**
高分子学报,2003,(1),1~6,-0001,():
-1年11月30日
以玉米淀粉和3,5-二硝基苯甲酰氯为原料合成了一种新型肌酐吸附剂并采用红外光谱、元素分析、核磁共振等手段对产物化学结构进行了表征,考察了3,5-二硝基苯甲酸淀粉酯对肌酐的静态吸附性能,建立了3,5-二硝基苯甲酸与肌酐络合产物的结构模型,初步探索了3,5-二硝基苯甲酸淀粉酯对肌酐吸附机理* 结果表明,3,5-二硝基苯甲酸淀粉酯对肌酐有较好的吸附性能,吸附在4h内完成,吸附容量随3,5-二硝基苯甲酸淀粉酯的取代度的增大而提高;在肌酐溶液浓度为0~300mg·L-1,吸附容量亦随肌酐浓度增大而提高;吸附温度从19℃升高到37℃时,吸附容量呈现降低的趋势;吸附容量随溶液pH值的增长呈现先增加后降低的趋势,在pH=8左右达到最大;在肌酐溶液浓度为100mg·L-1,吸附温度为37℃、介质pH=7的条件下,3,5-二硝基苯甲酸淀粉酯对肌酐的最大吸附量达25mg·g-1.
肌酐,, 吸附剂,, 络合物,, 3,, 5-二硝基苯甲酸淀粉酯
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【期刊论文】Synthesis and Application of Starch 3,5-Dinitrobenzoate
于九皋, Jiugao Yu, Dongzhi Yang
Starch/St,-0001,():
-1年11月30日
A novel starch ester was prepared by the reaction of starch and 3,5-dinitrobenzoyl chloride (DNBZ-Cl). The product (starch 3,5-dinitrobenzoate, DNBZ-ST) was characterized by means of elemental analysis, Fourier Transform Infrared (FTIR) and 13C NMR spectroscopy. The influences of molar ratio of DNBZ-Cl to anhydroglucose (AGU), reaction temperature and time, and amount of pyridine on the degree of substitution (DS) were studied. The esterification reaction is essentially complete after 2h. Increase in the molar ratio of DNBZ-Cl to AGU leads to an increase in DS when the former varies from 2:1 to 5:1. DS increases with the reaction temperature when the latter is varied from 70 to 100 ℃. DS first increases and then decreases with amount of pyridine, the highest DS was obtained when V(pyridine)/m(starch) was 53mL/g. The thermal stability of DNBZ-ST increases when the DS increases, and the degradation starts at 353℃ for the sample of DS 2.14. Creatinine is a toxin accumulated in the blood of chronic renal failure (CRF) patients and a special adsorbent for creatinine is not reported in literature. DNBZ-ST displayed specific adsorption ability for creatinine, the adsorption equilibrium is reached after 4h. The adsorption capacity increases with the DS of adsorbent and creatinine concentration. When the creatinine concentration is higher than 300mg/L, concentration has no apparent effect on the adsorption capacity. As the temperature of the solution is varied from 19 to 49 ℃, adsorption capacity first decreases and then increases, being lowest at 37℃. The dsorption capacity first increases and then decreases as the pH value increases, and is highest at pH 8.The highest adsorption capacity obtained was 25mg of creatinine per gram of adsorbent at 37℃, pH 7 and a creatinine concentration of 100mg/L. The study on the FTIR and UV-VIS spectra suggested that some chemical reaction took place between the DNBZ-ST and creatinine in buffer solution.
Starch 3,, 5-dinitrobenzoate, Adsorbent, Creatinine
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于九皋, 王晓东
高分子学报,2001,(1),99~104,-0001,():
-1年11月30日
本文选用Fe3+-油酸的组合物为降解剂,研究它与淀粉、聚乙烯共混体系在模拟堆肥温度(70℃)下的热氧化降解行为,对其力学性能、分子量下降率及氢过氧化物浓度进行跟踪测试,并通过扫描电子显微镜(SEM)及x-射线衍射仪(XRD)对试样的表面形态和结晶性能进行表征实验结果表明:含有Fe3+的有机化合物降解剂在实验条件下对试样有明显的促降解作用,并且高Fe+3含量的降解剂催化PE基体降解活性的发挥受环境因素特别是氧气浓度高低的影响不敏锐,而低Fe3+含量的降解剂则与之相反在上述实验事实的基础上推导出该体系中聚乙烯热氧化降解的动力学方程式.
聚乙烯,, 淀粉,, Fe+, -油酸,, 热氧化降解
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【期刊论文】聚乙烯/多价态金属有机化合物体系的低温降解行为*
于九皋, 陈崧哲
高分子学报,2000,(4),482~485,-0001,():
-1年11月30日
Metallic organic compounds of iron, stannum and manganese were introduced into lowdensity polyethylene as catalysts of degradation at low temperatures. The mechanical properties, viscosity-average molecular weight of polyethylene and the hydropeoxide concentration in the matrix were measured, It was shown that at 70℃ the adopted additives can catalyze the degradation of polyethylene efficeienty. After 60 day's aging, most of the samples became very fragile, and their molecular weight decreased in large scales. The relationship between molecular weght and hydroperoxide concentration, as well as the mode of the degrading behavior of the prepared matries, was also discussed.
聚乙烯,, 低温降解,, 多价态金属有机化合物,, 氢过氧化物
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于九皋, JIUGAO YU, HANSHENG LI, MINQIU ZHANG, MINLIAN ZHANG
Journal of Applied Polymer Science, Vol. 75, 523-527 (2000),-0001,():
-1年11月30日
In this article, the degradation mechanism of PE films containing additives with metal ions at a simulated composting temperature has been studied. The hy-droperoxide concentration [POOH] in the films was traced quantitatively by using the iodometric potentiometric titration, compared with Fourier transform infrared spec-trometry (FTIR). The results show that [POOH] increases during the early stage of degradation, followed by a more or less flat maximum before it starts to decrease. At the same time, similar results are obtained by the FTIR analysis. Besides, it is found that the rate laws for the carbonyl index and [POOH] increases seem more complicated, instead of an exponential-type increase in the early stage of the oxidation. When they are fitted by polynomial equations, the greater the rate of degradation, the more the number and content of the high-power members in the polynomial.
polyethylene, metal ion, compost, degradation
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